US4529559A - Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid - Google Patents
Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid Download PDFInfo
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- US4529559A US4529559A US06/620,940 US62094084A US4529559A US 4529559 A US4529559 A US 4529559A US 62094084 A US62094084 A US 62094084A US 4529559 A US4529559 A US 4529559A
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- phosphorus trichloride
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- 238000000034 method Methods 0.000 title claims abstract description 19
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000002253 acid Substances 0.000 title claims abstract description 9
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002576 ketones Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- NAISYYJIARZUIC-UHFFFAOYSA-N 3,4-dihydronaphthalen-1-ylphosphonic acid Chemical compound C1=CC=C2C(P(O)(=O)O)=CCCC2=C1 NAISYYJIARZUIC-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- -1 acetophenone Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- LVEKJWLAJJVWIT-UHFFFAOYSA-N cyclohexen-1-ylphosphonic acid Chemical compound OP(O)(=O)C1=CCCCC1 LVEKJWLAJJVWIT-UHFFFAOYSA-N 0.000 description 1
- ZDYPUHLWRYGWPO-UHFFFAOYSA-N ethenyl phosphono hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)OC=C ZDYPUHLWRYGWPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YOKDQEBPBYOXHX-UHFFFAOYSA-N prop-1-en-2-ylphosphonic acid Chemical compound CC(=C)P(O)(O)=O YOKDQEBPBYOXHX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/383—Cycloaliphatic acids
Definitions
- the present invention relates to a process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid by reacting a ketone with phosphorus trichloride at elevated temperatures.
- Vinylphosphonic acid and its derivatives have gained commercial interest as material which can be polymerized to compounds of high molecular weight or processed together with further polymerizable compounds to give a copolymer.
- 1-phenylvinyl-1-phosphonic acid its homopolymer and copolymers with other vinyl compounds are used for aftertreating phosphated metal surfaces, for example (cf. German Specification DE-OS No. 24 55 624 and DE-OS No. 26 15 489).
- a known process for making substituted vinylphosphonic acids comprises reacting a ketone with phosphorus trichloride in the presence of glacial acetic acid (Houben-Weyl, Methoden der organischen Chemie XII/1, 363-4 (1963). During the reaction, acetyl chloride and hydrogen chloride are split off and presumably cyclic phosphonic acid is obtained which is hydrolyzed to give 1-hydroxyalkane-1-phosphonic acid as an intermediary product which in turn is dehydrated by heating it in an inert solvent, such as 1,1,2,2-tetrachloroethane, to give the desired substituted vinylphosphonic acid (German Patent Specification DE-OS No. 20 60 218).
- an inert solvent such as 1,1,2,2-tetrachloroethane
- the process of this invention comprises more particularly: reacting a ketone with phosphorous acid and phosphorus trichloride in a molar ratio of 2:1:1, if desired in an inert solvent, at temperatures between 20° and 150° C., preferably 40°-120° C., 1 mol phosphorous acid being incidentally replaceable by a further mol phosphorus trichloride and 3 mols water so that altogether 1 mol phosphorus trichloride is added to a mixture of ketone and water in the molar ratio of 1:1.5,
- the ketone should preferably be mixed with the phosphorous acid, the mixture should be heated to reaction temperature and the phosphorus trichloride should be slowly added in metered proportions, resulting hydrogen chloride being allowed to escape.
- a preferred feature provides for the ketone to be used in an excess.
- the ketone in excess either serves as a reactant and simultaneously as a solvent, or it is used to ensure the formation of a final product containing but little residual phosphorous acid in excess.
- a further optional feature of the present process provides for the ketone and phosphorus trichloride to be used in a molar ratio larger than or equal to 1:1, if desired in the inert solvent, and for water, namely for 1.5 mols water, to be added thereto. Needless to say it is possible for 50% of the phosphorus trichloride and for the water to be replaced by the corresponding quantity of phosphorous acid.
- a reactive ketone e.g. acetophenone
- it is a vinylpyrophosphonic acid which is predominantly produced and which can be hydrolyzed with the use of stoichiometric quantities of water to give the corresponding vinylphosphonic acid, if desired.
- the crude product initially obtained is thermally aftertreated, prior to or after hydrolysis. To this end, the reaction product is heated over a period of 1 to 60 minutes to a temperature between the reaction temperature and 250° C. The respective minimum temperature depends on the reactivity of the ketone used.
- the ketone is selected from compounds of the following general formula ##STR1## in which R and R' being identical or different each stand for hydrogen or a halogen-substituted or unsubstituted alkyl, aryl, alkaryl or aralkyl group having from 1 to 18 carbon atoms, and R" stands for an alkyl, aryl, alkaryl or aralkyl group having from 1 to 18 carbon atoms.
- 1-(4-bromophenyl)-vinyl-1-phosphonic acid commenced crystallizing out from the solution in the form of colorless needles.
- 85 g (0.32 mol) phosphonic acid was separated corresponding to a yield of 80.8%. By recycling the mother liquor, it was possible further to improve the yield.
- 31 P-NMR-spectroscopy indicated that it was composed of 91.2 weight % 1-phenylvinyl-1-phosphonic acid, 1.9 weight % 1-hydroxy-1-phenylvinyl-1-phosphonic acid, 5.1 weight % phosphorous acid and 1.8 weight % phosphoric acid.
- 31 P-NMR-spectroscopy indicated that the product (based on the anhydrous final product) was composed of about 95 weight % 1-phenylvinyl-1-phosphonic acid and inter alia of about 1.4 weight % phosphoric acid and about 1.2 weight % phosphorous acid.
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- Organic Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The disclosure relates to a process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid by reacting a ketone with phosphorus trichloride in the presence of phosphorous acid by using the ketone, phosphorous acid and phosphorus trichloride in a molar ratio of 2:1:1, 1 mol phosphorous acid being replaceable by a further mol phosphorus trichloride and 3 mols water.
Description
The present invention relates to a process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid by reacting a ketone with phosphorus trichloride at elevated temperatures.
Vinylphosphonic acid and its derivatives have gained commercial interest as material which can be polymerized to compounds of high molecular weight or processed together with further polymerizable compounds to give a copolymer.
1-phenylvinyl-1-phosphonic acid, its homopolymer and copolymers with other vinyl compounds are used for aftertreating phosphated metal surfaces, for example (cf. German Specification DE-OS No. 24 55 624 and DE-OS No. 26 15 489).
A known process for making substituted vinylphosphonic acids comprises reacting a ketone with phosphorus trichloride in the presence of glacial acetic acid (Houben-Weyl, Methoden der organischen Chemie XII/1, 363-4 (1963). During the reaction, acetyl chloride and hydrogen chloride are split off and presumably cyclic phosphonic acid is obtained which is hydrolyzed to give 1-hydroxyalkane-1-phosphonic acid as an intermediary product which in turn is dehydrated by heating it in an inert solvent, such as 1,1,2,2-tetrachloroethane, to give the desired substituted vinylphosphonic acid (German Patent Specification DE-OS No. 20 60 218).
This process comprising several intermediate stages is very expensive.
We have now unexpectedly found that vinylphosphonic acid derivatives are considerably more easily obtainable by substituting phosphorous acid for glacial acetic acid in the above process.
The process of this invention comprises more particularly: reacting a ketone with phosphorous acid and phosphorus trichloride in a molar ratio of 2:1:1, if desired in an inert solvent, at temperatures between 20° and 150° C., preferably 40°-120° C., 1 mol phosphorous acid being incidentally replaceable by a further mol phosphorus trichloride and 3 mols water so that altogether 1 mol phosphorus trichloride is added to a mixture of ketone and water in the molar ratio of 1:1.5, The ketone should preferably be mixed with the phosphorous acid, the mixture should be heated to reaction temperature and the phosphorus trichloride should be slowly added in metered proportions, resulting hydrogen chloride being allowed to escape.
A preferred feature provides for the ketone to be used in an excess. In this case, the ketone in excess either serves as a reactant and simultaneously as a solvent, or it is used to ensure the formation of a final product containing but little residual phosphorous acid in excess.
A further optional feature of the present process provides for the ketone and phosphorus trichloride to be used in a molar ratio larger than or equal to 1:1, if desired in the inert solvent, and for water, namely for 1.5 mols water, to be added thereto. Needless to say it is possible for 50% of the phosphorus trichloride and for the water to be replaced by the corresponding quantity of phosphorous acid.
In those cases in which a reactive ketone, e.g. acetophenone, is used, it is a vinylpyrophosphonic acid which is predominantly produced and which can be hydrolyzed with the use of stoichiometric quantities of water to give the corresponding vinylphosphonic acid, if desired.
In those cases in which a less reactive ketone is used, the crude product initially obtained is thermally aftertreated, prior to or after hydrolysis. To this end, the reaction product is heated over a period of 1 to 60 minutes to a temperature between the reaction temperature and 250° C. The respective minimum temperature depends on the reactivity of the ketone used. The ketone is selected from compounds of the following general formula ##STR1## in which R and R' being identical or different each stand for hydrogen or a halogen-substituted or unsubstituted alkyl, aryl, alkaryl or aralkyl group having from 1 to 18 carbon atoms, and R" stands for an alkyl, aryl, alkaryl or aralkyl group having from 1 to 18 carbon atoms.
The process of this invention would not have been expected even by the expert and compares favorably with prior art methods. More particularly, it is no longer necessary to use an auxiliary, such as acetic acid, and the otherwise invariable formation of by-products e.g. acetyl chloride, is avoided. It has already been suggested (German Specification DE-OS No. 31 25 329) that derivatives of vinylphosphonic acid or vinylpyrophosphoric acid should be prepared by reacting a ketone with tetraphosphorus hexoxide in the presence of catalytic amounts of a proton-donating substance, such as H3 PO3, but this process cannot be commercialized. The reason resides in the fact that tetraphosphorus hexoxide is a product which is not commercially available, but has to be made in the laboratory in troublesome and expensive manner and in addition to this is generally contaminated with elemental yellow phosphorus.
The following Examples illustrate the invention which is naturally not limited thereto.
79.6 g (0.4 mol) p-bromacetophenone and 16.4 g (0.2 mol) phosphorous acid in 100 ml toluene were introduced into a 500 ml multi-necked flask provided with a reflux condenser, thermometer, agitator and dropping funnel and heated to 90°-100° C. Next, 27.5 g (0.2 mol) phosphorus trichloride was added dropwise within 30 minutes with moderate admission of heat. After a post-reaction period of 10 minutes at boiling temperature, the pyro-compound was hydrolyzed by the addition of 3.6 g (0.2 mol) water. After a further post-reaction period of 10 minutes, the whole was allowed to cool. After cooling, 1-(4-bromophenyl)-vinyl-1-phosphonic acid commenced crystallizing out from the solution in the form of colorless needles. 85 g (0.32 mol) phosphonic acid was separated corresponding to a yield of 80.8%. By recycling the mother liquor, it was possible further to improve the yield.
43.2 g (0.3 mol) α-tetralone and 12.1 g (0.15 mol) phosphorous acid in 90 ml toluene were introduced into an apparatus as described in Example 1 and heated to 90°-120° C. Next, 20.3 g (0.15 mol) phosphorus trichloride was added dropwise, and the whole was then allowed to undergo post-reaction over a period of 30 minutes at boiling temperature. After cooling to 70° C., the whole was hydrolyzed with 2.7 g (0.15 mol) water. After cooling, 56 g (0.27 mol) 3,4-dihydronaphthalene-1-phosphonic acid was separated, corresponding to a yield of 90%. By recycling the mother liquor, it was possible to increase the yield to more than 90%.
80.4 g (0.67 mol) acetophenone and 27.5 g (0.335 mol) phosphorus acid in 100 ml methylene chloride were introduced into an apparatus as described in Example 1 and heated to boiling. Next, 46.1 g (0.335 mol) phosphorus trichloride was added within 50 minutes. 6.2 g (0.34 mol) water was added, the solvent was distilled off and the residue was heated for 10 minutes to 150° C. 120 g crude product was separated. 31 P-NMR-spectroscopy indicated that it was composed of 91.2 weight % 1-phenylvinyl-1-phosphonic acid, 1.9 weight % 1-hydroxy-1-phenylvinyl-1-phosphonic acid, 5.1 weight % phosphorous acid and 1.8 weight % phosphoric acid.
184 g (1.53 mols) acetophenone and 41.4 g (2.3 mols) water were introduced into an apparatus as described in Example 1 and heated to 80° C. 210.8 g (1.53 mols) phosphorus trichloride was added dropwise while the temperature was increased to 100° C. towards the end of the dropwise addition. The product was hydrolyzed with 13.9 g (0.77 mol) water and heated for 5 minutes to 150° C. 279 g reaction product was separated. 31 P-NMR-spectroscopy indicated that it was composed of 87% 1-phenylvinyl-1-phosphonic acid and inter alia of 4% phosphorous acid.
144 g (1.2 mols) acetophenone and 137.5 g (1 mol) phosphorus trichloride were introduced into an apparatus as described in Example 1. The addition of water was started at room temperature. 27 g (1.5 mols) water was added within 35 minutes, the reaction temperature finally reaching 100° C. with gentle supply of heat. Ketone in excess was removed at 150° C. in a water jet vacuum. 141 g crude product was obtained; it was hydrolyzed with 80 ml water and diluted to give 221 g aqueous solution. 31 P-NMR-spectroscopy indicated that the product (based on the anhydrous final product) was composed of about 95 weight % 1-phenylvinyl-1-phosphonic acid and inter alia of about 1.4 weight % phosphoric acid and about 1.2 weight % phosphorous acid.
49 g (0.5 mol) cyclohexanone and 20.5 g (0.25 mol) phosphorous acid in 100 ml toluene were introduced into an apparatus as described in Example 1 and heated to 90° C. Next, 34 g (0.25 mol) phosphorus trichloride in 50 ml toluene was added dropwise. The solvent was distilled off and the crude product was heated for 2 minutes to 200° C. After cooling to 100° C., the crude product was hydrolyzed with 4.5 g (0.25 mol) water and taken up in glacial acetic acid. 50 g (0.3 mol) cyclohexene-1-phosphonic acid crystallized from the acetic acid solution. This corresponded to a yield of 61.7%.
300 ml acetone and 27 g (1.5 mols) water were introduced into an apparatus as described in Example 1 and heated to boiling. Next, 137.5 g (1 mol phosphorous trichloride was added dropwise. After a post reaction period of 10 minutes at boiling temperature, the whole was hydrolyzed with 20 ml water; the solvent phase was separated from the resin formed which was subsequently heated for 2 minutes to 200° C. 92 g product was obtained. 31 P-NMR-spectroscopy indicated that the product consisted essentially of 75 weight % propene-2-phosphonic acid and 25 weight % phosphorous acid.
Claims (8)
1. A process for making a vinyl or substituted vinyl phosphonic or -pyrophosphonic acid from a ketone, comprising:
reacting the ketone with (a) phosphorus trichloride and (b) phosphorus acid or a partial or total replacement for phosphorus acid, said partial or total replacement for phosphorus acid being the combination of phosphorus trichloride with 3 moles of water for each mole of phosphorus trichloride in said partial or total replacement, the reaction being carried out in an inert solvent in the ketone: (a):(b) molar ratio of 2:1:1.
2. A process according to claim 1, wherein the ketone has the formula: ##STR2## wherein R and R' are identical or different and each stands for hydrogen or a halogen-substituted or unsubstituted alkyl, aryl, alkaryl, or aralkyl group having from 1 to 18 carbon atoms, and R" stands for an alkyl, aryl, alkaryl, or aralkyl group having from 1 to 18 carbon atoms.
3. A process for making vinylphosphonic acids or vinylpyrophosphonic acids by reacting a ketone with phosphorus trichloride at elevated temperatures which comprises: effecting the reaction in the presence of phosphorous acid by using at least two moles of ketone for every mole of phosphorous acid and every mole of phosphorus trichloride, 1 mol phosphorous acid being replaceable by a further mole phosphorus trichloride and 3 mols water.
4. The process as claimed in claim 3, wherein the ketone is mixed with phosphorous acid, the mixture is heated and phosphorus trichloride is metered thereinto.
5. The process as claimed in claim 3, wherein the reaction is carried out in the presence of a solvent.
6. The process as claimed in claim 5, wherein an excess of ketone is used as the solvent.
7. The process as claimed in claim 5, wherein the solvent is inert toward the reactants.
8. The process as claimed in claim 3, wherein the reaction is carried out at temperatures between 20° and 150° C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3323392 | 1983-06-29 | ||
| DE19833323392 DE3323392A1 (en) | 1983-06-29 | 1983-06-29 | METHOD FOR PRODUCING DERIVATIVES OF VINYLPHOSPHONIC OR VINYLPYROPHOSPHONIC ACIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4529559A true US4529559A (en) | 1985-07-16 |
Family
ID=6202667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/620,940 Expired - Fee Related US4529559A (en) | 1983-06-29 | 1984-06-15 | Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4529559A (en) |
| EP (1) | EP0130439B1 (en) |
| JP (1) | JPS6023389A (en) |
| DD (1) | DD220605A5 (en) |
| DE (2) | DE3323392A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391816A (en) * | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
| US6429329B1 (en) | 1995-02-10 | 2002-08-06 | Akzo Nobel Nv | Synthesis of a hydrocarbylvinylphosphonic acid hydrocarbyl ester |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3517970A1 (en) * | 1985-05-18 | 1986-11-20 | Hoechst Ag, 6230 Frankfurt | CARBOXYTETRALIN PHOSPHONIC ACIDS AND A METHOD FOR THE PRODUCTION THEREOF |
| US5783730A (en) * | 1997-05-02 | 1998-07-21 | Akzo Nobel Nv | Formation of styrene phosphonic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2254124A (en) * | 1939-06-05 | 1941-08-26 | Du Pont | Organic compound of quinquevalent phosphorus |
| US2694684A (en) * | 1951-12-11 | 1954-11-16 | Standard Oil Dev Co | Lubricating oil compositions |
| SU899565A1 (en) * | 1980-03-21 | 1982-01-23 | Ордена Ленина Институт Элементоорганических Соединений Ан Ссср | Process for producing alpha-hydroxyphosphine acids |
| EP0068350A1 (en) * | 1981-06-27 | 1983-01-05 | Hoechst Aktiengesellschaft | Process for preparing derivatives of vinyl phosphonic or vinyl pyrophosphonic acids |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2060218C3 (en) * | 1970-12-08 | 1980-06-04 | Hoechst Ag, 6000 Frankfurt | Process for the preparation of 1-phenyl-vinyl-1-phosphonic acid |
| DE2060259C3 (en) * | 1970-12-08 | 1980-01-03 | Hoechst Ag, 6000 Frankfurt | Phenyl vinyl phosphonic acids and processes for their production |
| DE3130628A1 (en) * | 1981-08-01 | 1983-02-17 | Röhm GmbH, 6100 Darmstadt | SUBSTITUTED 1-PHENYL-VINYL-1-PHOSPHONIC ACIDS AND THEIR USE |
-
1983
- 1983-06-29 DE DE19833323392 patent/DE3323392A1/en not_active Withdrawn
-
1984
- 1984-06-15 EP EP84106863A patent/EP0130439B1/en not_active Expired
- 1984-06-15 DE DE8484106863T patent/DE3463144D1/en not_active Expired
- 1984-06-15 US US06/620,940 patent/US4529559A/en not_active Expired - Fee Related
- 1984-06-27 JP JP59131219A patent/JPS6023389A/en active Granted
- 1984-06-27 DD DD84264589A patent/DD220605A5/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2254124A (en) * | 1939-06-05 | 1941-08-26 | Du Pont | Organic compound of quinquevalent phosphorus |
| US2694684A (en) * | 1951-12-11 | 1954-11-16 | Standard Oil Dev Co | Lubricating oil compositions |
| SU899565A1 (en) * | 1980-03-21 | 1982-01-23 | Ордена Ленина Институт Элементоорганических Соединений Ан Ссср | Process for producing alpha-hydroxyphosphine acids |
| EP0068350A1 (en) * | 1981-06-27 | 1983-01-05 | Hoechst Aktiengesellschaft | Process for preparing derivatives of vinyl phosphonic or vinyl pyrophosphonic acids |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5391816A (en) * | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
| EP0653430A1 (en) * | 1993-11-08 | 1995-05-17 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
| US6429329B1 (en) | 1995-02-10 | 2002-08-06 | Akzo Nobel Nv | Synthesis of a hydrocarbylvinylphosphonic acid hydrocarbyl ester |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3323392A1 (en) | 1985-01-10 |
| JPS6023389A (en) | 1985-02-05 |
| JPH0421677B2 (en) | 1992-04-13 |
| EP0130439B1 (en) | 1987-04-15 |
| DD220605A5 (en) | 1985-04-03 |
| DE3463144D1 (en) | 1987-05-21 |
| EP0130439A1 (en) | 1985-01-09 |
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